Matrix photochemistry of syn-(Chlorocarbonyl)sulfenyl bromide, syn-ClC(O)SBr: Precursor to the Novel Species anti-ClC(O)SBr, syn-BrC(O)SCl, and BrSCl

ROSANA M. ROMANO; CARLOS O. DELLA VÉDOVA; ANTHONY J. DOWNS; TIM GREENE

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

Año: 2001 vol. 123 p. 5794 - 5801

0002-7863

The vapor of (chlorocarbonyl)sulfenyl bromide, ClC(O)SBr, was isolated in solid Ar, Kr, N2, and Ar doped with 5% CO at 15 K, and the matrix was subsequently irradiated with broad-band UV-visible light (200 e ì e 800 nm), the changes being followed by reference to the IR spectrum of the matrix. The initial spectrum showed the vapor of ClC(O)SBr to consist of more than 99% of the syn form (with the CdO bond syn with respect to the S-Br bond) in equilibrium with less than 1% of the anti conformer. Irradiation caused various changes to occur. First, conformational randomization took place, leading to a roughly equimolar mixture of the two rotamers, and so affording the first spectroscopic characterization of an anti-ClC(O)Scontaining compound. Simultaneously, the novel constitutional isomer syn-BrC(O)SCl was also formed. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. compound. Simultaneously, the novel constitutional isomer syn-BrC(O)SCl was also formed. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. various changes to occur. First, conformational randomization took place, leading to a roughly equimolar mixture of the two rotamers, and so affording the first spectroscopic characterization of an anti-ClC(O)Scontaining compound. Simultaneously, the novel constitutional isomer syn-BrC(O)SCl was also formed. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. compound. Simultaneously, the novel constitutional isomer syn-BrC(O)SCl was also formed. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. syn with respect to the S-Br bond) in equilibrium with less than 1% of the anti conformer. Irradiation caused various changes to occur. First, conformational randomization took place, leading to a roughly equimolar mixture of the two rotamers, and so affording the first spectroscopic characterization of an anti-ClC(O)Scontaining compound. Simultaneously, the novel constitutional isomer syn-BrC(O)SCl was also formed. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. compound. Simultaneously, the novel constitutional isomer syn-BrC(O)SCl was also formed. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. various changes to occur. First, conformational randomization took place, leading to a roughly equimolar mixture of the two rotamers, and so affording the first spectroscopic characterization of an anti-ClC(O)Scontaining compound. Simultaneously, the novel constitutional isomer syn-BrC(O)SCl was also formed. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. compound. Simultaneously, the novel constitutional isomer syn-BrC(O)SCl was also formed. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. spectrum showed the vapor of ClC(O)SBr to consist of more than 99% of the syn form (with the CdO bond syn with respect to the S-Br bond) in equilibrium with less than 1% of the anti conformer. Irradiation caused various changes to occur. First, conformational randomization took place, leading to a roughly equimolar mixture of the two rotamers, and so affording the first spectroscopic characterization of an anti-ClC(O)Scontaining compound. Simultaneously, the novel constitutional isomer syn-BrC(O)SCl was also formed. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. compound. Simultaneously, the novel constitutional isomer syn-BrC(O)SCl was also formed. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. various changes to occur. First, conformational randomization took place, leading to a roughly equimolar mixture of the two rotamers, and so affording the first spectroscopic characterization of an anti-ClC(O)Scontaining compound. Simultaneously, the novel constitutional isomer syn-BrC(O)SCl was also formed. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. compound. Simultaneously, the novel constitutional isomer syn-BrC(O)SCl was also formed. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. syn with respect to the S-Br bond) in equilibrium with less than 1% of the anti conformer. Irradiation caused various changes to occur. First, conformational randomization took place, leading to a roughly equimolar mixture of the two rotamers, and so affording the first spectroscopic characterization of an anti-ClC(O)Scontaining compound. Simultaneously, the novel constitutional isomer syn-BrC(O)SCl was also formed. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. compound. Simultaneously, the novel constitutional isomer syn-BrC(O)SCl was also formed. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. various changes to occur. First, conformational randomization took place, leading to a roughly equimolar mixture of the two rotamers, and so affording the first spectroscopic characterization of an anti-ClC(O)Scontaining compound. Simultaneously, the novel constitutional isomer syn-BrC(O)SCl was also formed. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. compound. Simultaneously, the novel constitutional isomer syn-BrC(O)SCl was also formed. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. (200 e ì e 800 nm), the changes being followed by reference to the IR spectrum of the matrix. The initial spectrum showed the vapor of ClC(O)SBr to consist of more than 99% of the syn form (with the CdO bond syn with respect to the S-Br bond) in equilibrium with less than 1% of the anti conformer. Irradiation caused various changes to occur. First, conformational randomization took place, leading to a roughly equimolar mixture of the two rotamers, and so affording the first spectroscopic characterization of an anti-ClC(O)Scontaining compound. Simultaneously, the novel constitutional isomer syn-BrC(O)SCl was also formed. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. compound. Simultaneously, the novel constitutional isomer syn-BrC(O)SCl was also formed. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. various changes to occur. First, conformational randomization took place, leading to a roughly equimolar mixture of the two rotamers, and so affording the first spectroscopic characterization of an anti-ClC(O)Scontaining compound. Simultaneously, the novel constitutional isomer syn-BrC(O)SCl was also formed. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. compound. Simultaneously, the novel constitutional isomer syn-BrC(O)SCl was also formed. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. syn with respect to the S-Br bond) in equilibrium with less than 1% of the anti conformer. Irradiation caused various changes to occur. First, conformational randomization took place, leading to a roughly equimolar mixture of the two rotamers, and so affording the first spectroscopic characterization of an anti-ClC(O)Scontaining compound. Simultaneously, the novel constitutional isomer syn-BrC(O)SCl was also formed. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. compound. Simultaneously, the novel constitutional isomer syn-BrC(O)SCl was also formed. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. various changes to occur. First, conformational randomization took place, leading to a roughly equimolar mixture of the two rotamers, and so affording the first spectroscopic characterization of an anti-ClC(O)Scontaining compound. Simultaneously, the novel constitutional isomer syn-BrC(O)SCl was also formed. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79Br/81Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs 35Cl/37Cl and 79